EP0667878B1 - Copolyacetals sequences, leur procede de preparation et leur utilisation dans des detergents et des nettoyants - Google Patents

Copolyacetals sequences, leur procede de preparation et leur utilisation dans des detergents et des nettoyants Download PDF

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EP0667878B1
EP0667878B1 EP93924547A EP93924547A EP0667878B1 EP 0667878 B1 EP0667878 B1 EP 0667878B1 EP 93924547 A EP93924547 A EP 93924547A EP 93924547 A EP93924547 A EP 93924547A EP 0667878 B1 EP0667878 B1 EP 0667878B1
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block
polyacetals
groups
polyacetal
mol
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EP0667878A1 (fr
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Matthias Kroner
Gunnar Schornick
Richard Baur
Volker Schwendemann
Heinrich Hartmann
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3711—Polyacetal carboxylates

Definitions

  • the invention relates to block copolyacetals, processes for their preparation and their use in detergents and cleaning agents.
  • polyacetals which are obtainable by cationically initiated polyaddition of divinyl ethers and dihydroxy compounds and optionally monohydroxy compounds, as addition to low-phosphate and phosphate-free detergents and cleaning agents is known.
  • polyacetals are known, which are obtainable by cationically initiated polyaddition of divinyl ethers and dihydroxy compounds and subsequent addition of monohydroxy compounds to 5 to 95% of the vinyl ether groups in the polyacetal, so that the resulting polyacetals have vinyl ether groups.
  • the present invention has for its object to provide new substances that can be used in detergents.
  • the block copolyacetals obtainable in this way are used as additives for low-phosphate and phosphate-free detergents and cleaning agents and as low-foam surfactants in dishwashing detergents.
  • Polyacetals of group (A) containing at least 2 OH groups in the molecule and containing acetaldehyde acetal units are prepared, for example, by subjecting (a) divinyl ether and (b) dihydroxy compounds in a molar ratio of 1: 2 to 1: 1,0001 to a cationically initiated polyaddition. In this cationically initiated polyaddition, monohydroxy compounds can optionally be added as a further group (c).
  • Suitable monomers of group (a) are divinyl ether, furan, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, bis- (hydroxypropyl ether) from 250 to 4,500, polyethylene glycol divinyl ether with molecular weights of polyethylene glycol up to 20,000, polypropylene glycol divinyl ether with molecular weights up to 10,000, and divinyl ethers of copolymers of ethylene oxide and propylene oxide with molecular weights up to 10,000, and divinyl ethers of diols which can be obtained by elimination of water from polyols , for example.
  • Dihydroxy compounds are used as monomers of group (b).
  • groups for example alkylene glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols up to molecular weights of 10,000, propylene glycol, dipropylene glycol, polypropylene glycols with molecular weights up to 10,000, copolymers of ethylene oxide and Propylene oxide and optionally butylene oxide with molecular weights up to 10,000, polytetrahydrofuran with molecular weights up to 10,000, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, neopentyl glycol, 1,5-pentanediol , 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol,
  • alkylene glycols such as
  • those dihydroxy compounds which also carry further functional groups for example ester, amide, nitrile, ether, acetal, imidoester, ketone, imide, can also be used as group (b) monomers. and thioether groups as well as CC double or CC triple bonds.
  • suitable compounds of this type are tartaric acid dimethyl ester, tartaric acid diethyl ester, 2,2-bis (hydroxymethyl) propionic acid methyl ester, hydroxypivalic acid neopentyl glycol ester, 2-butene-1,4-diol and 3-hexyne-2,5-diol, terephthalic acid bis (ethylene glycol ester), 1-phenylethylene glycol, octadecanediol from hydrogenated castor oil.
  • Examples of other suitable monomers of group (b) are dihydroxycarboxylic acid esters which can be isolated from natural fats and oils or can be prepared by means of enzymatic, bacterial or chemical reactions, for example from rapeseed oil, linseed oil or castor oil.
  • Examples of such compounds are dihydroxy fatty acids such as 10,12-dihydroxystearic acid, 9,10-dihydroxystearic acid, 9,12-dihydroxy-10-octadecenoic acid, 9,12-dihydroxy-9-oxo-10-octadecenoic acid, 10,13-dihydroxy-11 -octadecenoic acid and 12,13-dihydroxy-9-oxo-10-octadecenoic acid.
  • Dihydroxy fatty acid esters can also be obtained by hydroxylating and oxidizing fatty acids of natural origin, for example from ricinoleic acid, linoleic acid, oleic acid, linolenic acid, elaidic acid, palmitoleic acid, myristoleic acid, palmitic acid and stearic acid.
  • Diols formed by the elimination of water from polyols such as, for example, dianhydrosorbitol, dianhydromannitol, dianhydroerythritol, are also suitable.
  • Monomers of group (b) used with preference are butanediol, hexanediol, diethylene glycol, polyethylene glycols up to molecular weights up to 20,000, triethylene glycol, dimethyl tartarate and diethyl tartarate.
  • Suitable monohydroxy compounds of group (c), which are optionally used in the cationically initiated polyaddition, are aliphatic and aromatic compounds, each having a hydroxyl group.
  • the aliphatic and aromatic compounds which normally contain hydroxyl groups and contain up to 30 carbon atoms in the molecule. These substances are primarily alcohols and phenols. However, they can also contain further functional groups, for example ester, amide, nitrile, ether, acetal, aminoester, imide and thioether groups and also contain CC double bonds and CC triple bonds.
  • Examples of compounds under consideration are C 1 - to C 30 -ein facede alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanols, 2-methylbutanol, 3-methylbutanol, tert .-Amyl alcohol, 3-methyl-3-pentanol, cyclohexanol, n-hexanol, n-octanol, isooctanol, decanol, dodecanol, stearyl alcohol and palmityl alcohol, and also oxo alcohols, which can be obtained by adding carbon monoxide and hydrogen to olefins using the oxo process, Allyl alcohol, phenol, o-, m- and p-cresol, alkylphenols, benzyl alcohol, propargyl alcohol, butinol, 3-methyl-3-
  • Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide and butylene oxides.
  • Suitable alkoxylation products are, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1,2-butylene glycol monomethyl ether, 2- (4-methoxyphenyl) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol conversion products, 3-molar products of methyl monobutyl ether, molar conversion methylene monoxide, 25 Oxo alcohol with 3 to 25 mol ethylene oxide.
  • Suitable monofunctional alcohols include ethylene chlorohydrin, propylene chlorohydrin, 6-chlorohexanol, 8-chlorooctanol, Glykolchuremethylester, ethyl glycolate, Nursingchenremethylester lactate, Nursing7:30reisopropylether, lactic acid n-butyl ester, lactic acid isobutyl ester, Mandelchuremethylester, mandelate, Hydroxipropionnitril, Hydroxibutterchuremethylester, hydroxybutyrate, hydroxyvalerate, Ethyl hydroxyvalerate, isopropyl hydroxyvalerate, methyl hydroxyisovalerate, ethyl hydroxyisovalerate, methyl hydroxyisobutyrate, ethyl hydroxyisobutyrate, methyl hydroxypivalate, hydroxypivalate ethyl, ethyl benzilate, Mandelonitrile, Hydroxymalonklathylester
  • hydroxy fatty acid esters which can be prepared bacterially, enzymatically or by chemical hydroxylation of oils or fats of natural origin, for example based on linoleic acid, linolenic acid, oleic acid, elaidic acid, ricinoleic acid, palmitic acid and stearic acid.
  • the monomers (a), (b) and optionally (c) are polymerized cationically.
  • the OH group of a monomer of group (b) adds to a vinyl ether group of the monomer of group (a) to form an acetaldehyde acetal of the structure
  • This polyaddition gives a polymeric main chain in which the monomer units are linked to one another via acetaldehyde acetal units.
  • the cationic copolymerization of the monomers of groups (a), (b) and optionally (c) can be initiated with all organic or inorganic acid-reacting substances.
  • Suitable cationic initiators are, for example, oxalic acid, tartaric acid, adipic acid, succinic acid, succinic anhydride, citric acid, formic acid, acetic acid, propionic acid, malic acid, mono- or poly-halogenated carboxylic acids, such as trifluoroacetic acid or trichloroacetic acid, hydrogen chloride, hydrogen bromide, hydrogen sulfonic acid, phosphoric acid, sulfuric acid, sulfuric acid -Toluenesulfonic acid, boric acid, ascorbic acid, acidic aluminum oxide, aluminum sulfate, potassium aluminum sulfate, iron II sulfate, iron III sulfate, aluminum oxide, titanyl sulfate, iron III chloride, boron trifluoride, boron trichloride, Boron tribromide, iodine, ion exchangers in the acid form and inert solids loaded with acid.
  • the initiators for the cationic polymerization are usually used in amounts of 0.001 to 20, preferably 0.01 to 1% by weight, based on the monomers of groups (a) and (b).
  • the copolymerization is very exothermic.
  • the reaction temperatures are between -20 and 250, preferably 0 to 200 ° C.
  • Oxalic acid, tartaric acid and citric acid are preferably used as polymerization initiators.
  • the monomers (a) and (b) react in the presence of 0.1 to 5% by weight of p-toluenesulfonic acid at 40 ° C. in an exothermic reaction within 10 minutes. completely. If 0.2% by weight of oxalic acid is used to initiate the copolymerization, the copolymerization is complete at 90 ° C. within 1 hour and at 130 ° C. within 10 minutes. However, it is also possible to let the copolymerization initiated by means of oxalic acid take place at 200 ° C. within a few seconds. In general, when initiating using weaker acids (tartaric acid, oxalic acid or citric acid), temperatures above 70 ° C.
  • weaker acids tartaric acid, oxalic acid or citric acid
  • the copolymerization usually produces colorless oils or resins that are very stable when using oxalic acid and tartaric acid as a catalyst.
  • the cationic polymerization of the monomers (a), (b) and optionally (c) is preferably carried out in the absence of a solvent.
  • a solvent it is also possible to work in the presence of inert diluents. This can be advantageous in certain cases because the heat of reaction can then be easily removed using the evaporating diluent.
  • a strong acid is used as the initiator, a solution of the initiator in a diluent is preferably used, for example a 0.005 to 10% by weight, particularly preferably a 0.01 to 5% by weight solution of p-toluenesulfonic acid in toluene.
  • Suitable diluents for cationic copolymerization are all diluents which do not have any functional groups which can react with vinyl ethers. Diluents which are readily available in anhydrous form and are not hygroscopic are preferably used.
  • Suitable diluents are ethyl acetate, diethylene glycol diethyl ether, ethoxyethyl acetate, butoxyethyl acetate, aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, n-heptane, n-octane and isooctane, and aromatic hydrocarbons, such as toluene, xylene, mesitylene, tetralin and anisole.
  • Suitable solvents are also tetrahydrofuran, dioxane and decalin, acetone, ethyl methyl ketone and cyclohexanone.
  • the copolymerization can be carried out, for example, as a one-pot reaction.
  • the monomers of groups (a) and (b) and optionally (c) can be mixed in a reaction vessel with the exclusion of atmospheric moisture, mixed with initiator and heated to the required reaction temperature.
  • the total amount of initiator is placed in the reaction vessel together with 10% of the monomer mixture of components (a), (b) and optionally (c) to be polymerized at 20 ° C. and the polymerization reaction is preferably started under an inert gas atmosphere by heating the in the reaction vessel submitted components. The mixture is stirred and also during the subsequent copolymerization.
  • the remaining monomer mixture of the compounds of components (a), (b) and (c) is added continuously or batchwise to the extent that the heat of polymerization can be safely removed.
  • oxalic acid, tartaric acid or citric acid is used as the initiator, temperatures of about 70 to about 160 ° C. are required to start the copolymerization of the monomers (a), (b) and optionally (c). The acids then dissolve in the monomer mixture to form a homogeneous solution and the polymerization begins.
  • the heterogeneous reaction mixture is heated to a temperature in the range from 100 to 250 ° C. until the polymerization starts.
  • the initiator is either separated off or deactivated. Deactivation of the catalyst is recommended because the copolymers are subject to hydrolysis with molecular weight reduction in the presence of acidic substances and water or other protic solvents.
  • the reaction mixture is mixed with alkalis, preferably sodium bicarbonate, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, potassium carbonate, ammonium carbonate, amines, such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, after completion of the copolymerization and, if appropriate, after the reaction mixture has cooled.
  • Calcium oxide is also suitable for deactivating the acidic initiators, Calcium hydroxide, basic aluminum oxide and basic ion exchanger. Insoluble initiators can easily be removed by filtration.
  • polyacetals containing at least 2 OH groups in the molecule are formed which contain acetaldehyde acetal units. If, on the other hand, the compounds of components (a) and (b) described above are used in a molar ratio of 2: 1 to 1,0001: 1, polyacetals containing acetaldehyde acetal units and having at least 2 vinyl ether groups in the molecule are formed. This group of compounds is the group (B) polyacetals.
  • the polyacetals of groups (A) and (B) preferably have K values from 10 to 100 (determined according to H. Fikentscher in 1% strength solution in tetrahydrofuran at 25 ° C.).
  • reaction of the polyacetals (A) with the polyacetals (B) can be illustrated schematically, for example, as follows:
  • a hydrophilic polyacetal B is produced from 4 mol of triethylene glycol divinyl ether and 3 mol of triethylene glycol and has 7 monomer units which are linked via acetyaldehyde acetal units.
  • the hydrophilic polyacetal B has terminal vinyl ether groups.
  • a block copolyacetal is formed from 7 hydrophilic monomer units, to which hydrophobic blocks of 3 monomer units have been added on both sides.
  • the block copolyacetal consists of 13 monomer units, with hydrophobic structures at the end and hydrophilic structural elements in the middle. This block copolyacetal has OH end groups.
  • hydrophilic block I 1 with terminal OH groups on both sides with a hydrophilic block I 2 with terminal vinyl ether groups.
  • Additional hydrophilic macromers I 3 which carry OH groups, can be attached to this hydrophilic block, which is made up of 2 different hydrophilic blocks: I 3 -I 2 -I 1 -I 2 -I 3
  • the polyacetal of 3 different hydrophilic blocks (I 1 , I 2 , I 3 ) has OH groups at the ends, which can be reacted with hydrophobic blocks O with terminal vinyl ether groups: OI 3 -I 2 -I 1 -I 2 -I 3 -O
  • the block copolyacetal has a hydrophilic core consisting of 3 different blocks I 1 , I 2 , I 3 and hydrophobic ends O. Due to the wide range of possible variations, the possible combinations are almost unlimited.
  • the properties of the block copolyacetals can be varied by the order in which the polyacetals (A) and (B) are reacted with one another. If one considers as an example the reaction of polyacetals from (A) with polyacetals (B) in such a ratio that the polyacetals A have 2 mol-OH end groups and the polyacetals (B) have 1 mol of vinyl ether end groups, the addition of ( A) to (B) at the beginning of the reaction, ie as long as vinyl ether groups are still present, polymers in the order BAB with vinyl ether groups terminated on both sides.
  • the order of uniting the blocks can be any.
  • the properties of the resulting block polyacetals can be adjusted in a targeted manner by varying the order in which the polyacetals A and B are added to the reaction mixture.
  • polymer surfactants can be produced.
  • the block copolyacetals are hydrolysed at pH values below 7 in acetaldehyde and diols. If the block copolyacetals are dissolved in water which is saturated with carbon dioxide, the block copolyacetals dissolved therein are virtually quantitatively split within 4 weeks. At a pH of 2, the hydrolysis of the block copolyacetals in aqueous media is complete within a few minutes.
  • the block copolymers can also be broken down by specific acid hydrolysis to give special To generate properties. It is also possible, for example, to subject block copolyacetals containing ester groups to alkaline hydrolysis in an aqueous medium in order to convert the block copolyacetals ester groups to carboxylate groups.
  • the block copolymers have, for example, K values in the range from 9 to 100 (determined according to H. Fikentscher in water at pH 8 at 25 ° C. and a polymer concentration of one percent by weight).
  • the molecular weight of the block copolymers (determined by viscometric measurements on aqueous solutions with polyethylene glycols as the standard) is preferably 300 to 150,000.
  • the block copolymers and their hydrolysis products are readily biodegradable.
  • the block polyacetals are used as additives to powdery or liquid low-phosphate and phosphate-free detergents and cleaning agents. They are also suitable as low-foaming surfactants in dishwashing detergents.
  • the amounts used in detergents and cleaning agents for block copolyacetals are usually in the range from 0.5-20, preferably 2 to 10, in dishwashing detergents, machine cleaners 0.1 to 40% by weight.
  • Low-phosphate washing and cleaning agents are to be understood as meaning those formulations which contain less than 25% by weight of phosphate, calculated as pentasodium triphosphate.
  • the composition of powder detergent formulations can vary widely. Phosphate-free detergent formulations, particularly concentrated, powdery compact detergents can contain zeolite and / or layered silicates in the form of crystalline or amorphous powdered hydrated soda water glasses in addition to the usual surfactant components as builders. Silicates of this type are known, cf. EP-B-0164514 and EP-A-0444415. The same applies to the composition of detergent formulations.
  • Detergent and cleaning agent formulations usually contain surfactants in amounts of 1 to 50% by weight, in some cases even higher amounts of surfactant, and possibly builders. This information applies to both liquid and powder detergent formulations. Examples of the composition of washing formulations which are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) in tabular form and in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160. Further information on the composition before washing and cleaning agents can be found in WO-A-90/13581.
  • the block copolyacetals to be used in detergents and cleaning agents according to the invention improve the primary washing capacity of low-phosphate and phosphate-free detergents and cleaning agents, can be incorporated into these formulations without problems, lower the viscosity of water-containing surfactants and result in stable, homogeneous detergent and cleaning agent formulations.
  • the block copolyacetals to be used according to the invention are important auxiliaries in the production of phosphate-reduced and phosphate-free detergents and cleaning agents.
  • the slurry concentration in the crutcher can be increased to at least 80%. This means better economy through cheaper utilization of the spray tower and a saving in energy because less water has to be evaporated.
  • the block copolyacetals and copolymers according to the invention can likewise be used advantageously wherever a gel phase is run through in the production of mixtures, which causes disturbances because of their high viscosity.
  • the block copolyacetals can also be used as emulsifiers and protective colloids for the preparation of dispersions. They are also suitable for use as polymeric plasticizers in materials such as polyvinyl chloride or polystyrene.
  • the block copolyacetals can also be used as flowable diol components for the production of polyurethanes.
  • a preferred application of the block copolyacetals is their use as low-foam surfactants in dishwashing detergents and in bottle washing, i.e. they are used both for cleaning textiles and for cleaning hard surfaces.
  • the block copolymers are stable to alkaline ingredients in formulations and, because of their adhesive properties, can also be used as water-soluble adhesives or raw materials for the production of water-soluble adhesives.
  • the percentages in the examples are percentages by weight.
  • the K values were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932) in a 1% strength by weight solution in water at pH 8 at 25 ° C.
  • Block copolyacetal 1 Preparation of a block copolyacetal of the type O-I-O with vinyl ether end groups
  • the polyacetal A is a hydrophilic block I and is prepared by dissolving 0.4 g of oxalic acid in 0.7 mol (105 g) of triethylene glycol at a temperature of 110 ° C. in a 500 ml round-bottomed flask and with within 2 hours 0.6 mol (94.8 g) of diethylene glycol vinyl ether were added continuously. The reaction mixture is kept at a temperature of 110 ° C. for a further 30 minutes and then a sample is taken in order to determine the residual content of vinyl ether groups iodometrically. It was 0.003 mol of vinyl ether groups.
  • the OH number of polyacetal A is 68 (calculated 56).
  • the polyacetal is a flowable resin with a K value of 15.1.
  • the block copolymer A described above is added to the polyacetal B within 2 hours directly after the preparation and the reaction is carried out at a temperature of 110.degree. After the addition of polyacetal A has ended, the reaction mixture is kept at a temperature of 110 ° C. for a further 40 minutes.
  • the vinyl ether content determined iodometrically on a sample is 0.12 mol of vinyl ether groups.
  • the block copolymer has a K value of 20.2.
  • This block copolyacetal is a (OI) n copolymer.
  • the polyacetal A forms the hydrophilic block I of the block copolyacetal. It is prepared according to the procedure given in Example 1 for the preparation of polyacetal A.
  • the polyacetal B is a hydrophobic block O which is obtained by dissolving 0.2 g of oxalic acid in 0.3 mol (42.6 g) of 1,4 butanediol divinyl ether at a temperature of 110 ° C. in a 500 ml round-bottomed flask and 0.2 mol (23.6 g) of 1,6-hexanediol were continuously added to the mixture within 60 minutes. After the addition of hexanediol has ended, the reaction mixture is stirred at a temperature of 110 ° C. for a further 30 minutes. Analysis of a sample shows 0.11 mol of vinyl ether groups (calculated 0.10 mol).
  • the polyacetal A described in Example 1 which has a temperature of 110 ° C., is metered in continuously over 2 hours to the polyacetal B described above. After the addition has ended, the reaction mixture is heated to a temperature of 110 ° C. for a further 40 minutes. After this time, the vinyl ether group content was 0.001 mol. The resulting block copolymer has a K value of 25.7.
  • a polyacetal A is produced which forms the hydrophobic block O of the block copolymer.
  • 0.3 g oxalic acid is dissolved in 0.3 mol (43.2 g) bis (hydroxymethyl) cyclohexane at a temperature of 110 ° C in a 250 ml round-bottomed flask and continuously with 0.2 mol (56 g) 1,4-butanediol divinyl ether added.
  • the reaction mixture is then heated to 110 ° C. for a further 30 minutes. It has a vinyl ether group content of 0.001 mol.
  • the OH number is 65 (calculated 72) and the K value is 10.9.
  • the polyacetal B which is to become part of the block copolymer as a hydrophilic block I, is prepared by 0.5 g of oxalic acid in 0.55 mol (86.9 g) of diethylene glycol divinyl ether at a temperature of 110 ° in a 250 ml round-bottomed flask C dissolves and 0.5 mol (75 g) triethylene glycol is metered in continuously within 2 hours. After the addition of the triethylene glycol, the reaction mixture is stirred at a temperature of 110 ° C. for a further 30 minutes. The iodometrically determined content of vinyl ether groups is 0.08 mol (calculated 0.1 mol).
  • Polyacetal B is a flowable resin. It has a K value of 11.3.
  • the polyacetal B which has a temperature of 110 ° C., is metered in continuously over 2 hours to the polyacetal A at a temperature of 110 ° C. After the addition of the polyacetal B, the reaction mixture is stirred for a further 40 minutes at a temperature of 110 ° C.
  • the vinyl ether content of the block copolymer formed is then determined iodometrically. It is 0.003 mol of vinyl ether groups (calculated 0 mol).
  • the OH number of the block copolymer is 32 (calculated 28) and K value 16.0.
  • This block copolymer corresponds to type I-O-I-O-I and has OH end groups.
  • the polyacetal A which forms the hydrophilic block I of the block copolymer, is prepared by dissolving 2 g of oxalic acid in 2.7 mol (405 g) of triethylene glycol at a temperature of 110 ° C. in a 1000 ml round-bottomed flask and for this within 3 hours of 2.4 mol (380 g) of diethylene glycol vinyl ether were metered in continuously. After the addition of the divinyl ether, the reaction mixture is stirred for a further 30 minutes at a temperature of 110 ° C.
  • the polyacetal A obtainable in this way has a content of 0.005 mol of vinyl ether groups and an OH number of 55 (calculated 43).
  • the K value of polyacetal A is 12.5.
  • the polyacetal B which forms the hydrophobic block O of the block copolyacetal, is prepared by 0.5 g of oxalic acid in 1.2 mol (170.4 g) of 1,4-butanedivinyl ether at a temperature of 110 in a 500 ml round-bottom flask ° C dissolves and 1.0 mol (118 g) 1.6 hexanediol metered in over 60 minutes. After the addition of hexanediol has ended, the reaction mixture is heated to a temperature of 110 ° C. for 30 minutes. Thereafter, the content of vinyl ether groups is 0.37 mol (calculated 0.4 mol).
  • the polyacetal B has a K value of 16.3.
  • the polyacetal B which has a temperature of 110 ° C., is metered in and reacted continuously over 2 hours to the polyacetal heated to a temperature of 110 ° C. After the addition of polyacetal B has ended, the reaction mixture is stirred for a further 40 minutes at a temperature of 110.degree.
  • the oxalic acid used in the production of the polyacetals A and B is sufficient to produce the block copolyacetals from the polyacetals To catalyze A and B.
  • the block copolyacetal obtained in this way has a vinyl ether group content of 0.002 mol and an OH number of 15 (calculated 10).
  • the K value of the block copolyacetal is 23.0.
  • This block copolyacetal corresponds to the type OI 1 -II 1 -O with OH groups.
  • oxalic acid 0.4 g is dissolved in 0.6 mol (130.8 g) of triethylene glycol divinyl ether in a 500 ml round-bottomed flask, and 0.4 mol (82.4 g) of diethyl tartarate are added within 60 minutes. After the tartaric acid ester has been added, the reaction mixture is stirred for a further 45 minutes at a temperature of 110 ° C. and then a sample is taken from it, which is analyzed. 0.37 mol of vinyl ether groups are found iodometrically (calculated 0.4 mol).
  • the polyacetal B has a K value of 10.3.
  • oxalic acid is dissolved in 0.8 mol (114 g) of 1,4-butanediol divinyl ether at a temperature of 110 ° C. and within 60 minutes with 1.0 mol (118 g) 1 6-hexanediol continuously added at this temperature.
  • the reaction mixture is then stirred at 110 ° C. for a further 30 minutes.
  • the vinyl ether group content is determined iodometrically to be 0.006 mol.
  • the OH number is 96 (calculated 90).
  • the polyacetal A 1 has a K value of 13.5.
  • the polyacetal A which has a temperature of 110 ° C.
  • the polyacetal B which also has a temperature of 110 ° C.
  • the reaction is carried out at the temperature mentioned.
  • the reaction mixture is stirred at 110 ° C. for 60 minutes.
  • the vinyl ether group content is 0.18 mol (calculated 0.2 mol).
  • the block copolyacetal thus obtained is then metered in continuously to the polyacetal A1 heated to a temperature of 110 ° C. within 2 hours and then heated to 110 ° C. for a further 30 minutes.
  • the vinyl ether content of the block copolyacetal is 0.008 mol
  • the OH number is 18 (calculated 19).
  • block copolyacetals described above are tested as additives to detergents and cleaning agents.
  • the following examples demonstrate the influence of block copolyacetals on the primary washing effect and graying.
  • standard soiling fabric is washed several times together with white test fabric and the soiled fabric is renewed after each wash.
  • the dirt detached from the dirt fabric, which is drawn onto the white test fabric during washing, causes a drop in the degree of whiteness that is measured.
  • the whiteness differences on the individual fabrics are given before and after washing.
  • the block copolyacetals according to the invention markedly improve the primary washing action of the formulation. At the same time, an improvement in the graying inhibition is also observed. It should be taken into account here that due to the primary washing action, which is significantly improved by the block copolyacetals to be used according to the invention, there are higher dirt concentrations in the washing liquor and thus higher amounts of dirt are available for re-absorption. All of the polymers to be used according to the invention could be incorporated into the detergent formulation without problems and resulted in homogeneous, stable solutions.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Claims (4)

  1. Copolyacétals séquencés, caractérisés en ce que l'on peut les obtenir par la polyaddition cationiquement amorcée
    (A) de polyacétals contenant des unités acétaldéhydacétal avec au moins deux groupes OH dans la molécule et
    (B) de polyacétals contenant des unités acétaldéhydacétal avec au moins deux groupes vinyléther dans la molécule,
    où les séquences obtenues à partir des polyacétals A et B sont différentes et le rapport molaire des groupes OH dans les polyacétals (A) aux groupes vinyléther dans les polyacétals (B) varie de 2:1 à 1:2.
  2. Procédé de fabrication de copolyacétals séquencés, caractérisé en ce que l'on soumet
    (A) des polyacétals contenant des unités acétaldéhydacétal avec au moins deux groupes OH dans la molécule et
    (B) des polyacétals contenant des unités acétaldéhydacétal avec au moins deux groupes vinyléther dans la molécule,
    dans le rapport molaire des groupes OH dans les polyacétals (A) aux groupes vinyléther dans les polyacétals (B) de 2:1 à 1:2, à une polyaddition cationiquement amorcée, où les séquences obtenues à partir des polyacétals A et B sont différentes.
  3. Utilisation des copolyacétals séquencés selon la revendication 1 comme additifs pour des détergents de lavage et de nettoyage dépourvus de ou pourvus en phosphates.
  4. Utilisation des copolyacétals séquencés selon la revendication 1 comme agents tensioactifs ou surfactifs dans des produits de lavage de la vaisselle.
EP93924547A 1992-11-05 1993-10-29 Copolyacetals sequences, leur procede de preparation et leur utilisation dans des detergents et des nettoyants Expired - Lifetime EP0667878B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4237337 1992-11-05
DE4237337A DE4237337A1 (de) 1992-11-05 1992-11-05 Blockcopolyacetale, Verfahren zu ihrer Herstellung und ihre Verwendung in Wasch- und Reinigungsmitteln
PCT/EP1993/003018 WO1994010225A1 (fr) 1992-11-05 1993-10-29 Copolyacetals sequences, leur procede de preparation et leur utilisation dans des detergents et des nettoyants

Publications (2)

Publication Number Publication Date
EP0667878A1 EP0667878A1 (fr) 1995-08-23
EP0667878B1 true EP0667878B1 (fr) 1997-01-02

Family

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EP93924547A Expired - Lifetime EP0667878B1 (fr) 1992-11-05 1993-10-29 Copolyacetals sequences, leur procede de preparation et leur utilisation dans des detergents et des nettoyants

Country Status (8)

Country Link
US (1) US5466762A (fr)
EP (1) EP0667878B1 (fr)
JP (1) JPH08502775A (fr)
AT (1) ATE147088T1 (fr)
CA (1) CA2143745A1 (fr)
DE (2) DE4237337A1 (fr)
ES (1) ES2096956T3 (fr)
WO (1) WO1994010225A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4312753A1 (de) * 1993-04-20 1994-10-27 Basf Ag Verwendung von Polyacetalen zur Herstellung von kompostierbaren Formkörpern, als Beschichtungsmittel und als Klebstoff
EP1483362B2 (fr) * 2002-02-11 2012-12-26 Rhodia Chimie Composition detergente pour le lavage de la vaisselle comprenant un copolymere sequence
US7087702B2 (en) * 2002-10-15 2006-08-08 Dainippon Ink And Chemicals, Inc. Epoxy resin composition, process for producing epoxy resin, novel epoxy resin, novel phenol resin
US7677315B2 (en) 2005-05-12 2010-03-16 Halliburton Energy Services, Inc. Degradable surfactants and methods for use
US7662753B2 (en) 2005-05-12 2010-02-16 Halliburton Energy Services, Inc. Degradable surfactants and methods for use
US7608567B2 (en) 2005-05-12 2009-10-27 Halliburton Energy Services, Inc. Degradable surfactants and methods for use
US8951955B2 (en) * 2011-01-13 2015-02-10 Basf Se Use of optionally oxidized thioethers of alcohol alkoxylates in washing and cleaning compositions
EP3988634A1 (fr) 2020-10-23 2022-04-27 The Procter & Gamble Company Composition pour laver la vaisselle présentant une meilleure action moussante

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2252186A1 (de) * 1972-10-25 1974-05-16 Basf Ag Alkalistabile, oberflaechenaktive, schaumdaempfende mittel (acetale)
US4713441A (en) * 1986-08-01 1987-12-15 Sandoz Pharmaceuticals Corp. Polyacetal hydrogels formed from divinyl ethers and polyols
GB8924479D0 (en) * 1989-10-31 1989-12-20 Unilever Plc Detergent compositions
JPH03247614A (ja) * 1990-02-26 1991-11-05 Asahi Chem Ind Co Ltd ポリアセタールブロック共重合体及びその製法
DE4142130A1 (de) * 1991-12-20 1993-06-24 Basf Ag Verwendung von polyacetalen auf basis von vinylethern und dihydroxyverbindungen in wasch- und reinigungsmitteln und polyacetale

Also Published As

Publication number Publication date
WO1994010225A1 (fr) 1994-05-11
ES2096956T3 (es) 1997-03-16
JPH08502775A (ja) 1996-03-26
US5466762A (en) 1995-11-14
EP0667878A1 (fr) 1995-08-23
DE59305005D1 (de) 1997-02-13
ATE147088T1 (de) 1997-01-15
DE4237337A1 (de) 1994-05-11
CA2143745A1 (fr) 1994-05-11

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